Entropy-controlled cross-linking in linker-mediated vitrimers.

Recently developed linker-mediated vitrimers based on metathesis of dioxaborolanes with various commercially available polymers have shown both good processability and outstanding performance, such as mechanical, thermal, and chemical resistance, suggesting new ways of processing cross-linked polymers in industry, of which the design principle remains unknown [M. Röttger et al., Science 356, 62-65 (2017)]. Here we formulate a theoretical framework to elucidate the phase behavior of the linker-mediated vitrimers, in which entropy plays a governing role. We find that, with increasing the linker concentration, vitrimers undergo a reentrant gel-sol transition, which explains a recent experiment [S. Wu, H. Yang, S. Huang, Q. Chen, Macromolecules 53, 1180-1190 (2020)]. More intriguingly, at the low temperature limit, the linker concentration still determines the cross-linking degree of the vitrimers, which originates from the competition between the conformational entropy of polymers and the translational entropy of linkers. Our theoretical predictions agree quantitatively with computer simulations, and offer guidelines in understanding and controlling the properties of this newly developed vitrimer system.

Duality, Hidden Symmetry, and Dynamic Isomerism in 2D Hinge Structures.

Recently, a new type of duality was reported in some deformable mechanical networks that exhibit Kramers-like degeneracy in phononic spectrum at the self-dual point. In this work, we clarify the origin of this duality and propose a design principle of 2D self-dual structures with arbitrary complexity. We find that this duality originates from the partial central inversion (PCI) symmetry of the hinge, which belongs to a more general end-fixed scaling transformation. This symmetry gives the structure an extra degree of freedom without modifying its dynamics. This results in dynamic isomers, i.e., dissimilar 2D mechanical structures, either periodic or aperiodic, having identical dynamic modes, based on which we demonstrate a new type of wave guide without reflection or loss. Moreover, the PCI symmetry allows us to design various 2D periodic isostatic networks with hinge duality. At last, by further studying a 2D nonmechanical magnonic system, we show that the duality and the associated hidden symmetry should exist in a broad range of Hamiltonian systems.

Facilitated dynamics of an active polymer in 2D crowded environments with obstacles.

Understanding the behaviors of a single active chain in complex environments is not only an interesting topic in non-equilibrium physics but also has applicative implications in biological/medical engineering. In this work, by using molecular simulations, we systematically study the dynamical and conformational behaviors of an active polymer in crowded environments, i.e., a single active chain confined in 2D space with randomly arranged obstacles. We found that the competition between the chain's activity and rigidity in the presence of obstacles leads to many interesting dynamical and conformational states, such as the diffusive expanded state, the diffusive collapsed state, and the localized collapsed state. Importantly, we found a counter-intuitive phenomenon, i.e., crowded environments facilitate the diffusion of the active polymer within a large parameter space. As the crowdedness (packing fraction of obstacles) increases, the parameter space in which crowding-enhanced diffusion occurs still remains. This abnormal dynamics is attributed to a structural reason that the obstacles prevent active chains from collapsing. Our findings capture some generic features of active polymers in complex environments and provide insights into the design of novel drug delivery systems.

Hydrodynamics of random-organizing hyperuniform fluids.

Disordered hyperuniform structures are locally random while uniform like crystals at large length scales. Recently, an exotic hyperuniform fluid state was found in several nonequilibrium systems, while the underlying physics remains unknown. In this work, we propose a nonequilibrium (driven-dissipative) hard-sphere model and formulate a hydrodynamic theory based on Navier-Stokes equations to uncover the general mechanism of the fluidic hyperuniformity (HU). At a fixed density, this model system undergoes a smooth transition from an absorbing state to an active hyperuniform fluid and then, to the equilibrium fluid by changing the dissipation strength. We study the criticality of the absorbing-phase transition. We find that the origin of fluidic HU can be understood as the damping of a stochastic harmonic oscillator in q space, which indicates that the suppressed long-wavelength density fluctuation in the hyperuniform fluid can exhibit as either acoustic (resonance) mode or diffusive (overdamped) mode. Importantly, our theory reveals that the damping dissipation and active reciprocal interaction (driving) are the two ingredients for fluidic HU. Based on this principle, we further demonstrate how to realize the fluidic HU in an experimentally accessible active spinner system and discuss the possible realization in other systems.

Self-Assembly of Isostatic Self-Dual Colloidal Crystals.

Self-dual structures whose dual counterparts are themselves possess unique hidden symmetry, beyond the description of classical spatial symmetry groups. Here we propose a strategy based on a nematic monolayer of attractive half-cylindrical colloids to self-assemble these exotic structures. This system can be seen as a 2D system of semidisks. By using Monte Carlo simulations, we discover two isostatic self-dual crystals, i.e., an unreported crystal with pmg space-group symmetry and the twisted kagome crystal. For the pmg crystal approaching the critical point, we find the double degeneracy of the full phononic spectrum at the self-dual point and the merging of two tilted Weyl nodes into one critically tilted Dirac node. The latter is "accidentally" located on the high-symmetry line. The formation of this unconventional Dirac node is due to the emergence of the critical flatbands at the self-dual point, which are linear combinations of "finite-frequency" floppy modes. These modes can be understood as mechanically coupled self-dual rhombus chains vibrating in some unique uncoupled ways. Our work paves the way for designing and fabricating self-dual materials with exotic mechanical or phononic properties.

Supercrystallographic Reconstruction of 3D Nanorod Assembly with Collectively Anisotropic Upconversion Fluorescence.

Constructing three-dimensional (3D) metamaterials from functional nanoparticles endows them with emerging collective properties tailored by the packing geometries. Herein, we report 3D supercrystals self-assembled from upconversion nanorods (NaYF4:Yb,Er NRs), which exhibit both translational ordering of NRs and orientational ordering between constituent NRs in the superlattice (SL). The construction of 3D reciprocal space mappings (RSMs) based on synchrotron-based X-ray scattering measurements was developed to uncover the complex structure of such an assembly. That is, the two main orthogonal sets of hexagonal close-packing (hcp)-like SLs share the [110]SL axis, and NRs within the SL possess orientational relationships of [120]NR//[100]SL, [210]NR//[010]SL, and [001]NR//[001]SL. Notably, these supercrystals containing well-aligned NRs exhibit collectively anisotropic upconversion fluorescence in two perpendicular directions. This study not only demonstrates novel crystalline superstructures and functionality of NR-based 3D assemblies but also offers a unique tool for deciphering a wide range of complex nanoparticle supercrystals.

Hierarchical glass transition of hard hemidisks with local assemblies.

Using computer simulation, we investigate the glass transition of a two-dimensional hard-hemidisk system. Upon increasing the packing fraction of the system, we find that the system vitrifies into a glass with local assembled discal "dimers", which are free to rotate in a collective way. The rotational mean square displacement does not exhibit the typical plateau (slowdown) like what occurs in the translational mean square displacement. This effect induces a pronounced violation of the rotational Stokes-Einstein relationship compared with the translational degree of freedom at the supercooled region. However, the obtained glass transition points in these two freedom degrees are found to be the same within the numerical accuracy, which is due to the strong positive spatial and dynamic correlation between translational and rotational slow-moving particles. Moreover, we find that the locally assembled dimers can serve as fast rotating gears facilitating the orientational relaxation in the system, and this suggests that the locally favored finite structures play an important role in the hierarchical glass transition of anisotropic colloids.

Self-assembled multi-layer simple cubic photonic crystals of oppositely charged colloids in confinement.

Designing and fabricating self-assembled open colloidal crystals have become one major direction in the soft matter community because of many promising applications associated with open colloidal crystals. However, most of the self-assembled crystals found in experiments are not open but close-packed. Here, by using computer simulation, we systematically investigate the self-assembly of oppositely charged colloidal hard spheres confined between two parallel hard walls, and we find that the confinement can stabilize multi-layer NaCl-like (simple cubic) open crystals. The maximal number of layers of stable NaCl-like crystals increases with decreasing inverse screening length. More interestingly, at finite low temperature, the large vibrational entropy can stabilize some multi-layer NaCl-like crystals against the most energetically favoured close-packed crystals. In the parameter range studied, we find up to 4-layer NaCl-like crystals to be stable in confinement. Our photonic calculation shows that the inverse 4-layer NaCl-like crystal can already reproduce the large photonic band gaps of the bulk simple cubic crystal, which open in the low frequency range with a low dielectric contrast. This suggests new possibilities of using confined colloidal systems to fabricate open crystalline materials with novel photonic properties.

Correction: Driving dynamic colloidal assembly using eccentric self-propelled colloids.

Correction for 'Driving dynamic colloidal assembly using eccentric self-propelled colloids' by Zhan Ma et al., Soft Matter, 2017, 13, 8940-8946.

Complexation of Polyelectrolytes with Hydrophobic Drug Molecules in Salt-Free Solution: Theory and Simulations.

The delivery and dissolution of poorly soluble drugs is challenging in the pharmaceutical industry. One way to significantly improve the delivery efficiency is to incorporate these hydrophobic small molecules into a colloidal polyelectrolyes(PE)-drug complex in their ionized states. Despite its huge application value, the general mechanism of PE collapse and complex formation in this system has not been well understood. In this work, by combining a mean-field theory with extensive molecular simulations, we unveil the phase behaviors of the system under dilute and salt-free conditions. We find that the complexation is a first-order-like phase transition triggered by the hydrophobic attraction between the drug molecules. Importantly, the valence ratio between the drug molecule and PE monomer plays a crucial role in determining the stability and morphology of the complex. Moreover, the sign of the zeta potential and the net charge of the complex are found to be inverted as the hydrophobicity of the drug molecules increases. Both theory and simulation indicate that the complexation point and complex morphology and the electrostatic properties of the complex have a weak dependence on chain length. Finally, the dynamics aspect of PE-drug complexation is also explored, and it is found that the complex can be trapped into a nonequilibrium glasslike state when the hydropobicity of the drug molecule is too strong. Our work gives a clear physical picture behind the PE-drug complexation phenomenon and provides guidelines to fabricate the colloidal PE-drug complex with the desired physical characteristics.

Driving dynamic colloidal assembly using eccentric self-propelled colloids.

Designing protocols to dynamically direct the self-assembly of colloidal particles has become an important direction in soft matter physics because of promising applications in the fabrication of dynamic responsive functional materials. Here, using computer simulations, we found that in the mixture of passive colloids and eccentric self-propelled active particles, when the eccentricity and self-propulsion of active particles are high enough, the eccentric active particles can push passive colloids to form a large dense dynamic cluster, and the system undergoes a novel dynamic demixing transition. Our simulations show that the dynamic demixing occurs when the eccentric active particles move much faster than the passive particles such that the dynamic trajectories of different active particles can overlap each other while passive particles are depleted from the dynamic trajectories of active particles. Our results suggest that this is in analogy to the entropy-driven demixing in colloid-polymer mixtures, in which polymer random coils can overlap with each other while depleting the colloids. More interestingly, we find that by fixing the passive colloid composition at a certain value with increasing density, the system undergoes an intriguing re-entrant mixing, and the demixing only occurs within a certain intermediate density range. This suggests a new way of designing active matter to drive the self-assembly of passive colloids and fabricate dynamic responsive materials.

Transformable Superisostatic Crystals Self-Assembled from Segment Colloidal Rods.

Transformable mechanical structures can switch between distinct mechanical states. Whether this kind of structure can be self-assembled from simple building blocks at microscale is a question to be answered. In this work, we propose a self-assembly strategy for these structures based on a nematic monolayer of segmented colloidal rods with lateral cutting. By using Monte Carlo simulation, we find that rods with different cutting degrees can self-assemble into different crystals characterized by bond coordination z that varies from 3 to 6. Among these, we identify a transformable superisostatic structure with pgg symmetry and redundant bonds (z = 5). We show that this structure can support either soft bulk modes or soft edge modes depending on its Poisson's ratio, which can be tuned from positive to negative through a uniform soft deformation. We also prove that the bulk soft modes are associated with states of self-stress along the direction of zero strain during uniform soft deformation. The self-assembled transformable structures may act as mechanical metamaterials with potential applications in micromechanical engineering.

Dynamics of protein condensates in weak-binding regime.

Weak complementary interactions between proteins and nucleic acids are the main driving forces of intracellular liquid-liquid phase separation. The sticker-spacer model has emerged as a unifying principle for understanding the phase behavior of these multivalent molecules. It remains elusive how specific interactions mediated by stickers contribute to the rheological properties of the liquid condensates. Previous studies have revealed that for strong binding strength ɛ_{b}, the bulk diffusivity D depends on the effective bond lifetime τ, viz., D∝τ^{-1}. Consequently, equal concentrations of the complementary stickers induce a slow down in the dynamics of the condensates D∝e^{-1.5ɛ_{b}}. However, for weak-binding strength, it is expected that the resulting condensates are dynamic, loose network liquids rather than kinetically arrested, compact clusters. We develop a mean-field theory using the thermodynamics of the associative polymers and perform molecular-dynamics simulations based on the sticker-spacer model to study the controlling factors in the structure and dynamics of such condensates in the weak-binding regime. Through scaling analysis, we delineate how the free sticker fraction W_{f} and the bulk diffusivity D decrease with increasing binding energy and find that the internal dynamics of such network liquids are controlled by the free sticker fraction D∝W_{f}∝e^{-0.5ɛ_{b}} rather than the effective bond lifetime. Referred to as the free-sticker-dominated diffusivity, the microscopic slowdown due to a gradual loss of the free stickers affects the viscosity of the condensates as well, with the scaling of the zero-shear viscosity η∝e^{0.5ɛ_{b}}. Therefore, the way of controlling the structure, diffusivity, and viscosity of the condensates through the binding energy can be tested experimentally.

Barrier-controlled nonequilibrium criticality in reactive particle systems.

Nonequilibrium critical phenomena generally exist in many dynamic systems, like chemical reactions and some driven-dissipative reactive particle systems. Here, by using computer simulation and theoretical analysis, we demonstrate the crucial role of the activation barrier on the criticality of dynamic phase transitions in a minimal reactive hard-sphere model. We find that at zero thermal noise, with increasing the activation barrier, the type of transition changes from a continuous conserved directed percolation into a discontinuous dynamic transition by crossing a tricritical point. A mean-field theory combined with field simulation is proposed to explain this phenomenon. The possibility of Ising-type criticality in the nonequilibrium system at finite thermal noise is also discussed.

Mechanical Tolerance of Cascade Bioreactions via Adaptive Curvature Engineering for Epidermal Bioelectronics.

Epidermal bioelectronics that can monitor human health status non-invasively and in real time are core to wearable healthcare equipment. Achieving mechanically tolerant surface bioreactions that convert biochemical information to detectable signals is crucial for obtaining high sensing fidelity. In this work, by combining simulations and experiments, a typical epidermal biosensor system is investigated based on a redox enzyme cascade reaction (RECR) comprising glucose oxidase/lactate oxidase enzymes and Prussian blue nanoparticles. Simulations reveal that strain-induced change in surface reactant flux is the key to the performance drop in traditional flat bioelectrodes. In contrast, wavy bioelectrodes capable of curvature adaptation maintain the reactant flux under strain, which preserves sensing fidelity. This rationale is experimentally proven by bioelectrodes with flat/wavy geometry under both static strain and dynamic stretching. When exposed to 50% strain, the signal fluctuations for wavy bioelectrodes are only 7.0% (4.9%) in detecting glucose (lactate), which are significantly lower than the 40.3% (51.8%) in flat bioelectrodes. Based on this wavy bioelectrode, a stable human epidermal metabolite biosensor insensitive to human gestures is further demonstrated. This mechanically tolerant biosensor based on adaptive curvature engineering provides a reliable bio/chemical-information monitoring platform for soft healthcare bioelectronics.

Thermal-Disrupting Interface Mitigates Intercellular Cohesion Loss for Accurate Topical Antibacterial Therapy.

Bacterial infections remain a leading threat to global health because of the misuse of antibiotics and the rise in drug-resistant pathogens. Although several strategies such as photothermal therapy and magneto-thermal therapy can suppress bacterial infections, excessive heat often damages host cells and lengthens the healing time. Here, a localized thermal managing strategy, thermal-disrupting interface induced mitigation (TRIM), is reported, to minimize intercellular cohesion loss for accurate antibacterial therapy. The TRIM dressing film is composed of alternative microscale arrangement of heat-responsive hydrogel regions and mechanical support regions, which enables the surface microtopography to have a significant effect on disrupting bacterial colonization upon infrared irradiation. The regulation of the interfacial contact to the attached skin confines the produced heat and minimizes the risk of skin damage during thermoablation. Quantitative mechanobiology studies demonstrate the TRIM dressing film with a critical dimension for surface features plays a critical role in maintaining intercellular cohesion of the epidermis during photothermal therapy. Finally, endowing wound dressing with the TRIM effect via in vivo studies in S. aureus infected mice demonstrates a promising strategy for mitigating the side effects of photothermal therapy against a wide spectrum of bacterial infections, promoting future biointerface design for antibacterial therapy.

Nonequilibrium strongly hyperuniform fluids of circle active particles with large local density fluctuations.

Disordered hyperuniform structures are an exotic state of matter having vanishing long-wavelength density fluctuations similar to perfect crystals but without long-range order. Although its importance in materials science has been brought to the fore in past decades, the rational design of experimentally realizable disordered strongly hyperuniform microstructures remains challenging. Here we find a new type of nonequilibrium fluid with strong hyperuniformity in two-dimensional systems of chiral active particles, where particles perform independent circular motions of the radius R with the same handedness. This new hyperuniform fluid features a special length scale, i.e., the diameter of the circular trajectory of particles, below which large density fluctuations are observed. By developing a dynamic mean-field theory, we show that the large local density fluctuations can be explained as a motility-induced microphase separation, while the Fickian diffusion at large length scales and local center-of-mass-conserved noises are responsible for the global hyperuniformity.

Self-Assembled Chiral Photonic Crystals from a Colloidal Helix Racemate.

Chiral crystals consisting of microhelices have many optical properties, while presently available fabrication processes limit their large-scale applications in photonic devices. Here, by using a simplified simulation method, we investigate a bottom-up self-assembly route to build up helical crystals from the smectic monolayer of a colloidal helix racemate. With increasing the density, the system undergoes an entropy-driven cocrystallization by forming crystals of various symmetries with different helical shapes. In particular, we identify two crystals of helices arranged in binary honeycomb and square lattices, which are essentially composed of two sets of opposite-handed chiral crystals. Photonic calculations show that these chiral structures can have large complete photonic band gaps. In addition, in the self-assembled chiral square crystal, we also find dual polarization band gaps that selectively forbid the propagation of circularly polarized light of a specific handedness along the helical axis direction. The self-assembly process in our proposed system is robust, suggesting possibilities of using chiral colloids to assemble photonic metamaterials.

Three-Dimensional Non-Close-Packed Structures of Oppositely Charged Colloids Driven by pH Oscillation.

The implementation of non-close-packed structures in colloids is challenging. Using Brownian dynamics simulations, we study the nonequilibrium self-assembly in suspensions of oppositely charged particles, whose charge magnitude is responsive to the pH of the solution. Under the fast pH-oscillating condition, various non-close-packed (e.g., graphitelike and diamondlike) structures are obtained. Here, changing the amplitude of the pH oscillation is an effective way to fabricate colloidal dynamic structures. To clarify the underlying mechanism of the dynamic self-assembly, the analysis of effective potential is adopted. A dimensionless parameter, the ratio of effective repulsion and attraction, is introduced to reflect the subtle interactions in the system. We find that the imbalance between repulsion and attraction is the cause of structural diversity. Madelung energy is used to study the stability of these structures. Our results provide a new way to fabricate non-close-packed structures in colloids, which has potential applications in the synthesis of photonic crystals.

Modeling Stretching-Induced Immiscibility in Nonmonodisperse Polymer Systems.

The behavior of polymer chains under stretching is a classical problem in polymer science. However, a fundamental question still in mist is how the stretching affects the interactions between polymer chains, especially when the tensions on the chains are unequal. In this work, we combine statistical theory and molecular simulations to study the influence of this tension disparity on the miscibility of athermal polymer systems. Through a minimal model, we demonstrate that when polymer chains of different lengths are under the same stretching disparate tension states among polymer chains can lead to either macroscopic or microscopic phase separation, depending on whether their ending points are mobile or not. Generally, the immiscibility found here is an entropic effect arising from conformational asymmetry between unequally stretched polymer chains. Our findings provide a new mechanism to explain the flow-induced demixing in polymer blends and indicate that heterogeneous structure can occur during stretching, simply as a result of nonmonodispersity in elastic polymer materials.